Process of preparing pigmented nitrocellulose coating compositions



Patented Sept. 7, 1943 PROCESS OF PREPARING PIGMENTED INI- TROCELLULOSE COATING COMPOSITIONS Carrol A. Doran, Parlin, and Clarence It, De Bow, Jr., Penns Grove,.N. J., assignors' to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation-of Delaware No Drawing. Application December 19, 1940,

Serial No. 370,822

4 Claims. (61.210-203) This invention relates to a process of preparing grit and gel-free coating compositions and'more particularly to a process of preparing gritand gel-free pigmented nitrocellulose lacquers, and still .more particularly to a selective filtration of pigmented nitrocellulose lacquers.

It is necessary. in the. manufacture of pigmented nitrocellulose coating compositions to remove pigmentagglomerates and pigment aggregates as well as considerable gelatinous material in order to produce materials giving glossy, dry films. Nitrocellulose coating compositions or lacquers arecharacterized by their relatively high viscosity, which is due mainly to the presence of the nitrocellulose itself. Filtration of nitrocellulose compositions of all types has always presented numerous difficulties. Primarily these difiiculties-are due to the incompletely dissolved portions of nitrocellulose These gelatinous particles are normally soft and mobile so their shape can be greatlyv altered by the exertion .of pressure upon them, and they form a compressible filter cake. The particles tend to pass through the filtering medium unless they are trapped. This makes necessary the use of filtering media which have a pore size smaller than that of the apparent size of the normal gelatinous particle.

. These gel particles, while removable by use of a suitable filter medium, for example, afine felt cloth or filter paper, act to compress and to plug the pores of the filter medium rather than to build up a non-compressible porous cakeon the Commercial filter aidsaiormally contain parti-' cles having a great variety of shapes and sizes,

and the effective poresize is relatively small, so

small, in fact, that when dispersed pigments are presen't in the nitrocellulose compositions, a considerable portion of the pigment may remainon the filter bed after the filtering operation is completed. Also, the pigment particles tend toact somewhat as a filter aid when they form part of the filtering mass itself. Due to the fact that the dispersed pigment particles are normally smaller in size than the great majority of the filter aid,

- the effective pore size is greatly reduced and it is impo'ssibleto filter nitrocellulose enamels rapidly or in any quantity unless the filter is frequently cleaned.

' This invention has as an object the provision of positions. A still further object is the provision filter. When the materials being filtered include a dispersed pigment, the majority of whose particles being such that they can theoretically pass through the filtering medium selected, the formation of a gelatinous coating .on the pores of the true filter medium reduces the filtration efficiency enormously. Complete plugging of the system -is quickly reached as a result, and even during the active period of filtration there is some tend-, ency to remove useful pigment particles as the, effective pore size of the filter" medium is being reduced by the plugging action of the gels.

A means of trapping the gelatinous particles to prevent early plugging has been to add to the clear nitrocellulose composition a small portion of a filteraid such as diatomaceous earth, fIlI IGrS earth, or similar material. The relatively coarseparticles of the diatoxnaceou's earth build up, on a filter bed which may be'of fine wire,

paper, woven fabrics or felt or the like, and the gelatinous particles have a pronounced tendency to. stick tglthmparticles of filter aid rather than /cloggingthe pores of the filter medium. Thus, the addition of a filter aid to a clear nitrocellulose I composition improves its filtering characteristics. However, when dispersed pigment particles are added to a nitrocellulose composition, the filtratiori problem becomes much more diflicult.

of a filter mass having a pore size sufficiently large to pass substantially all of the highly dispersed pigment particles but small enough to trap gelled particles and also pigment aggregates and agglomerates visible to the naked eye. A further object is the selective filtration of pigmented cellulose derivative compositions. Other objects will appear hereinafter.

We have discovered that there exists a critical value in the effective pore size of the "filter aids below which it is impossible to secure continued and rapid filtration of pigmented nitrocellulose.

compositions, but above which rapid, continued possessed by the great majority of commercial diatomaceous filter aids and can be produced only by special processing. However, the methods of 'theaddition of filter aids to the pigmented composition being filtered and the considerable art developed in the use of filter aids has been utilized to no avail.

Before the importance of our discovery can be' appreciated fully it must be understood that normally filter aids are used to assist inthe removal of substantially all particles of a size sufficiently large to interfere with the transmission.

of a beam of light through the filtered liquid and medium. Pigmented compositions are basically designed to interfere with transmitted light and .gre'at numbers of particles are added to the nitrocellulose for this purpose. results. in the socalled hiding power of the composition.- :Thus, I either the technique of using commercial filteraids must be discarded and a new technique developedor advantage 'must be taken of our discovery that there is a'critical minimum effective pore size of filter'aid suitable for pigmented nitrocellulose compositions. The. first alternative has not been satisfactorily accomplished, and as a result commercial filteraids have not heretofore 4 been used for "the filtration of commercial pigmented nitrocellulose compositions.

It has-been found that when dirt particles and the particles of partially dissolved or. gelled nitrocellulose are to be removed from unpigmented nitrocellulose solutions, several of the commercially available filter aids having a small efi'ective- 'pore size willassi'st in the filtration. When the same filter aids are used with; pigmented nitrocellulose compositions, very'low through-puts are "obtained; that is, gallons of material per square foot of filtering area. Also, portions of'theuseful pigment particles are removed, resulting in a dis tinct waste of costly pigmenting material, a lower- 'ing of the hiding power of the enamel and often a simultaneous lowering of the durability of the enamel. The finely dispersed pig-.

-ments of thepresent practice havea particle size of one micron or less with few exceptered particles prevent easy grinding, and in this case many particles range in size from 1, to 5 microns, In the case of carbon black, the average size of a' finely dispersed particle is of the order of line micron distinguishable onlywith an electron microscope.

The average particle size of diatomaceous earth 1 f such as is found in Lompoc California deposits,is reported to bed the order of microns. It

' have been used in themanufacturing of the inground dry pigmentsfrom poor dispersion methods during incorporation of the dry pigments into the colloidal organic solution, tov what is often called mixing grit or to incompletely soluble nitrocellulose. Dirt also tends to accumulate during the various manufacturing operations.

r The careful filtration of pigmented nitrocellu lose compositions has been avoided heretofore,

termediate products. The clear or pigment-free nitrocellulose'base solutions areordinarily fil ,tere'd, oftentimes using filter aids. Thepigments are dispersed in resinsolutions by ball mill'grin'd- -ing, or mixed into high viscosity nitrocellulose .colloids by means of a heavy ,duty mixer, or the pigments are dispersed by milling into very stiff nitrocellulose colloids by means of heavy steel rolls. In all cases the eificiency of the dispersion is dependent ,upon the conditions used in the process, and in order to avoid .fine pigment grit in the finished enamel, the dispersion process is tions. Among the exceptions,' we have such Y pigments as the ultramarine blues in hich sin-' this particular operation.

would be assumed, therefore, that little difiiculty v would be encountered-indispersing the pigments having a particle size of 1 micron or less in a nitrocellulose composition and passing. them through a filter bed of this same diatomaceous earth. Practically, however, the diatomaceous earth contains definite portions of clay-like pareticles and considerable proportions of particles smaller than the 15 micron average size; It is also mesh.- This type of filtration removes dint, hairtrue that'. the particles ct, diatomaceous earth-have a great variety of shapes, so that in certain dimensions, for instance, inthe needle-like forms ates, agglutinates and .dirt particles from the pig- 'large enough they approach 1 micron orless, and in'building up a filter cake the average effective pore size is suchthat an appreciable proportionpf the finely dispersed pigment in'. the nitrocellulose compositions is trapped-on the filter bed.: This trapping of pigment particles inaddition to being waste- .ful, has the effect of lowering theefiiciency of the filter medium-in that only small amounts of enamel can be filtered beforethe rate of flowis reduced to a point that it is no longer economical to continue the filtration.

It is the principal object of this fvention to remove all'gelled particles, aggregates, agglomermented' nitrocellulose compositions which are in size to interfere-with the proper application of the coating composition or v to prevent .the realization of the optimum gloss and general appearance of the final dry film. These contaminants may result from the use of poorly 75 pores of the ge1atinous materia1 which quickly I undesirable particles.

often carried to extremes. Also, resin solutions used in the preparation of the enamels are set-' tledor filtered before addition to the final batch.

By a combination of preliminary dispersion processes and filtration steps the intermediate products are made substantially grit-free. These intermediate products are then blended ina predetermined order and mixed by highspeed, eflicient rotating paddle mixers, or their equivalents, until flow-outs or pours'of the enamels on metal or paper show that the mixing grit sa-called, has been reduced as far as it is possible to do so by It is at this point that it has a result of long experience, that approximately one-third of the enamels manufactured must still'be carefullyfiltered to further eliminate the of the enamel manufactured is ordinarily filtered by gravity through a wire screen of 60 .or 100 and much of any other contaminating material which may have entered the final mixer but does 'not remove pigment aggregates or mixing grit.

The wire screen filtration is not particularly difiicult. It is the fine filtration of enamels with which this invention is concerned.

. Contrary to the normal experience of the in-v dustry for other products, the use of the commercial pressure ty'pe filter presses, such as the Shriver plate and frame press, has not heretofore proved practical for pigmented nitrocellulose compositions because of the compressible cake formed, andfalthough several modifications have beenfsuggested, a very considerable proportion of l the filtration has been carried out by the socalled bag filters. I ple in-that an inner layer of felt and anouter layer of nainsook is tied on or wired on to a pipe leading from the bottom of the enamel mixer. 4

The enamel isallowed to fiow intothe bag under and squeezing of the bag is resorted to. This semi-mechanical operation is designed to free the been found, as

The remaining two-thirds These are fundamentally simaccumulates, part of this being displaced inside the bag and a small part forced through the pores of-the bag. The fact that some of the material is actuallybeing forced through renders the final product an incompletely filtered one.-

In a typical filtration of this type. and work'- ing with a black automotivenitrocellulose composition having a viscosity of approximately 2.5

poises at 25 C., it was found possible as the result of. several squeezing operations to obtains. total through-put of 22.6 gallons per square foot of effective filtering area. A pressure filtering operation'carried out on the same batch of. enamel through a small plate and frame press using the same felt and nainsook filtering-medium and using a final pressure of 50 pounds per square inch gave only 10.4 gallons per square foot. This nature of the filter cake formed.

' Filter aids of the diatomaceous with type ar available in a variety of grades ranging from the permeability coefllcient K in .the equation (D'Arcys lawfor porous media modified by introduction of the'term for the a olute viscosity.

. in poises).

- dV P K is'a constant, typical of the porous medium and independent of the liquid used. A is the crosssectional area of the filter cake, L; is the thicknessof the cake, V the volume of liquid passed in time in seconds 0, and P is the pressure diiferlow through-put is due to plugging of the pores r by the gel and by the spongy. easily compressible crude or raw diatom deposits which contain clay,

silts, etc., through selected grades. Other grades of filteraid represent chemically treated diatcmaceous earth or material which has been calcined sufficiently .to sinter the clayey components without fusing the diatom skeletons. In general,

the processing of the crude diatomaceous earth has as its object the control of the size distribution or the particles, and this is usually controlled by air separation or classifier processing. Normally the definition of the grade is dependent. uponwhat amounts to practical filtration experiments, that, is, for example, results secured when filteringa'sugar solution or other readily secured and reproducible-standard solution. a

The experiments are carried out by adding to the test liquid a small amount of the filter aid in' question. This is thoroughly mixed into the batch until a uniform suspension is secured.- The once across the cake in grams per square centimeter. All determinations of the permeability coefllcient, referred to herein, were made using C. P. acetone as the test liquid.

Acommercial diatoma-ceous filter aid recommended for the filtration of varnishes, resin solutions and clear nitrocellulose solutions was found by experiment to have a permeability coefficient of 1.63 10 for K, and in practical tests on clear nitrocellulose solutions gave a satisfactory rate of I both clears and enamels. The filtrationof'ciears batch is then pumped through afiltering medium such as felt or fine wire until a thin layer of the filteraid is caught by the filter medium producing a filter bed. The initialfiltered liquid is then returned to th starting tank in which agitation continues and .the filtration proper is started.

This is carried out by maintaining a' carefully regulated pressure and a constant temperature (in order to maintain a constant viscosity). The

rate of filtration or the through-put in a definite period of time is measured ingallons or pounds andiis normally expressed as gallons or poundsper square footof filter area. .The total through put is expressed-in'thesame manner but i independent of the time or rate of flow.-

In contrast to most filtrations wherein the object .is to remove substantially all solid. particles from the fluid or composition under treatment,

,, the filtration of nitrocellulose enamels is truly a selective process -We have found that contrary to the findings of previous investigators, filter aids of. the diatomaceous earth type can be advantageously usedtin the selective filtration of pigmented nitrocellulosesolutions, provided that the effective pore size of the filter aid is kept sufiiciently large.

Carman has described a method for determining the permeability coeflicient of a diatomaceous 1 filter-aid in the J ournal of- Industrial 8i Engineering Chemistry, .volume '31- (1049-1050) and es.- tablishes the reliability of this value as a measure tomaceousearth. The term effective pore size" as used in this specification is one which cannot of the screen was to prevent forcing the felt into filter am, having a permeability coeflicient of" 3.4 10- was mixed with a black nitrocellulose enamel under test to the amountof 0.15% by' through-put.

proceeded at a more rapid rate than when using the finer material. Also, a gain occurredin total However, when used with black enamels, although the initial rate of through-put was higher than in the case of the finer grade,

clogging quickly occurred and considerably less material was filtered per square foot of filter cloth than when the simple bag filter was used.

It was not until a grade of diatomaceous earth filter aid having a permeability coefficient of at least about 3.0 10- was used that the real ad vantages of the use of filter aids with enamels was establishedand the through-puts rose above those obtained with the, simple bag filter.

. Example 1 To illustrate the diil'erence'in practical use,fil-

trations were carried out using a. 'shriver-piate' press, the plates having an available filtering area I of 6.52 square feet. A single layer of Continental D 2.'felt was used as the filtering medium, being placed over a coarse wire screen. The purpose the channeled platesof the press. Diatomaceous weight based upon the total weight of the enamel.

@The-enamelhad a viscosityof approximately 2 Q poises at 25 C. Prior to the .actualdetermination of through-put and rate of now; asmall mo.unt of enamel plus filter 'aid was passed through the press and returned to the stora etank; started the formation of a cake of the filter, aid on the felt filtering material. The

enamel was then forced-through the system by a pump. The pressure usedat the start, was 15 pounds per square inch and this was gradually of the effective pore sizes formed by a bed of diaincreased-to 50 pounds per squar inch. The totalthrough-put represented all. the mater. al

passed through .(not counting the initial me;

be expressed in definite dimensions but refers to coating) until the rate of new through the press had practically ceased at the 50 pounds per square Total through-put was 987 v inch pressure. pounds per square foot of filter area.

' A filtrationcarried out on the same .enamel,-

using the conventional felt and nainsook bag and without filter aid, gave a through-put off384 pounds per square foot before excessive clogging occurred. In this operation the bag was squeezed at regular intervals to stimulate the fiow .rate."

' Example 2 gUtilizin-g a maroon pigmented nitrocellulose enamel, a grade of filter aid having a K of 1.63Xlwas compared with a grade having a K value 'of 3.l The particular maroon tested representedan' enamel extremely difficult to filter in anyway due to the difiicultiesof dis-' persing this type of pigment. The tests were made utilizing a. standard Shriver press using 5-7" plates having a total area of 2 .5 square feet.

at C." of appr'oximatelyl5 poises.

One-half pound of diatomaceous earth was added per'100 pounds of enamel. The viscosity of the enamel at 25 C. was approximately '10 poises. The maximum pressure in each case was 100 pounds per square inch.

- Through- K of diatomaceous earth moxie- V Example 3 Anexperiment was carried the filtration'of a black enamel having a viscosity 'A small Shriver plate press was used, the filtering area of .which was' square'foot. -In one portion .of

enamel a diatomaceous earth having a K- of 3.1 10- was added at the rate of.0.5 pound per 100 pounds of enamel. In the secondexperiment the enamel was-filtered-asreceived. The two oi. enamel took place. 'diatomaceous earth, plugging occurred in- 50 filtrations were carried out under carefully controlled conditions and untilat a pressure of 50 pounds per square inch no further marked fiow minutes and after'62 poundsp'er squarefoothad passed through. The filtration utilizing the filter aid continued'for 4 hours and'4'0 minutes and gave a total through-put of- 209 pounds per square foot of filtering area. The rates of fiow were substantially equal up to the plugging of the firstfilter'f This is important because it is the total through-put. which largely measures the economic worth-of filtrations.

The quantity of material to be-removed in the filtration of pigmented nitrocellulose compositions varies from batch tobatch. ,Also, there is littlechance of predicting what the filtration characteristics-of a new.'formulation will be. We have-found that regardless of the way in which thepigmented compositions are manufactured or regardless of the materials usd -in their formaid having a permeability constant K of'at least about 3'.0 10--" willmake economical the selective'filtration of pigmented nitrocellulose composition's over a. wide viscosityrange. The value 3.0x 10- for K represents a lower practical operating limit, the existence of which had not' been suspected. As the :va'lueoi "the permeability constant K increases beyond the critical value of 25. is to trap the gelatinous-particles on its surface, and thus to prevent the gels from entering the fine capillary pores of the finalffiltering mediu'm, whatever this may consist 'of. The'filter' aid on which the gelhas been deposited eventuout in two parts, on

3.o 1 oboth the rate or new and the throughput continues to improve, and we prefer to use a filter aid having as high a. value for K' as it. is possible to obtain. We are limited, hOWEVQLbY several considerations including the :iifiiculty of securing filter aidshaving the larger effective pore sizes, the difficulty of maintaining a uniform suspension of the-filter aid during the filtering. cycle and especially the undeniable'consideration that when the effective pore size becomes sum-.-

ciently great, the smaller pigment aggregates o'r agglomerates will pass through and the quality of tne enamel will be afiected.

We have found that for the and that at values for K as high as.4.5 10

quality products can .be produced. We prefer to' make use of filter aids having permeability coefflcients in the range of -3.0 10 to4.5 10 and when the finest degree of filtration is' required to between 3.0 10- and 4.0 10 However; in many special cases K values greater than 4.5 10 can be satisfactorily used.

One of the principal functions of the filter aid ally approaches the filtering medium which by this time is a combination of the base filtering medium plus a layer of coated-filter aid. It is here that the second principal function of the filter aid takes place. The filter aid dilutes the gelatinous residue preventing its coalescing to form a continuous film and whenpresent in the optimum amount tends to-form a porous, granular, practically incompressible cake, the pores of which are sufiiciently large to allow the-filtration to continue, As this cake builds up, the length of the pores increase and more pressure is required to maintain the rate of filtration at a "suitable value. It is also true that the effective pore In the absence of the size decreases steadily as the filtration is con-- 'tinued because.the filter aid is.-not completely efiective in its operation. This gradual decrease in pore size,.can be at least partially compensated for by increasing thepressure applied. Finally a point is reached at'whichthe rate of filtration is greatly reduced, and either a. limit has been reached in the pressure available. or. the effective pores have become so small that useful pigment particles are being removed from the enamel.

- Thew quantity of filter aid required will 'normally represent 0.5 or lessbased upon the total weight of solution to be filtered. A good average figure for pigmented nitrocellulose compositions in which the pigment is mainly carbon black has been found to be 0.2%. by weight: Sufilcient should be present in any'case to enttap the gelatinous material, so that a granularcake fo'rms' 'ulation, the use of ;a. diatomaceous earth filter during the-actual filtering operation.' Excessive amounts'only tend to build up thick filter cakes compositi'onsthrough the cake.

The use of diatomaceous filter aids' is dependent I I upon thorough mixing with thepigmented nitrocellulose composition before filtration is. started.

and some-continued agitation maybe required to prevent settling of the filter aids,.especially when the viscosity ofthe composition'is low. It

is occasionally preferable to form a me-coat.

with'a layer of diatomaceous earth formed on a supporting medium provided the snilicient dihighest quality enamels, filter aids having a value for K between 1' Z l.'0 10- and 4.0 10- are eminently satisfactory I which increase the pressure required to push the the equivalents of the olderwool felts in effective pore-size- A great variety of paper filtering mediums arealso available. The selection of a suitable base material will depend upon a number of factors including as nost important in the selective filtration of pigmented compositions, an effective pore size large enough to pass the useful pigment particles. It is not necessary in all i cases to use a material for backing capable of producing a satisfactory filtered product in the absence of the filter aid, as by prefiltering a first portioma cake of filter aid, w i!l be built up having the correct efiective pore size. It. will be seen that a variety-of filtering media can be used.

It is also possible to use filter aids with permeabiiity constants well above 3.0 as we depend upon ourfilter-aid to trap the gelatinous particles andin this -function the great variety of shapes present in diatomaceous earth and their surface irregularities make it the ideal medium,

am practice to use filter aids for clear nitrocellulose solutions and lacquer and to filter in standard Shriver presses.

The use of a diatomaceous earth having a per-- meability 'coeflicient of 3.0)(10- or more; made possible the filtration of pigmented "compositions in standard plate and frame presses'and equivalent equipment and greatly reduced the cost' of filtration. More uniform products are produced and when necessary products of improved quality and gloss can be produced. It permits the elimination of a number of relatively crude alternative filtering methods. duced is distinctly granular and can'be readily removed from a felt cloth, resulting in making possible reuse'of the cloth in many cases. In addition to the special selective straining of filtering action of the coarse filteraid, its use gives a siderable amount of compressibility is possible and as the pressure is increased there is pounced-increase inresistance. Y

. It s to be. understoodthat the foregoing debut only provided that in the self-packing characteristics of the diatomaceous earth the effective pores formed correspond to a stant of at least 3.0 10- V The use of the filter aids have proven to be most eifective when the cake remains in contact with the support material so that this support.

is protected from the deposition of fresh gelat- In a continuously operating filinous material. ter, means can be provided for keeping the 'cake below a'predetermined thickness by removing the top layer but, in generahcomplete removal of the filter aid cake at any point during the filtration will disturb the filtering efiiciency. This might occur in the bagfilter previously described.

permeability con where it is poor practice both from the angle'of total through-put as well as the dangerof forcing particles of the filter aid into the final product. The use of these coarse filter aids is most eil'ective in filtering systems where relatively high pressures can be applied.

- Our discovery makes possible the rapid, efii cient selective filtration of pigmented nitrocellulose J solutions. It permits the substantially complete removal of pigment aggregates and agglomerates of a size great enough to interfere with the gloss of the coatings when applied and dried. Its selective operation permits substantially all of theuseful, finely dispersed pigment to pass through pigmented nitrocellulose coating composition by high degree of nonecompressibility because of the strength'and rigidity of the silica particles of the diatomaceous earth. Here the pressure is. taken by the filter aid, which packs on the supporting medium, and the resistance-to fiow is independ ent of. the pressure. whereas with the sludge from,

the pigmented nitrocellulose compositions a contailed description is given byway of illustration and that many variationsmay bemade'therein' without tion.

We claimz' -1 The'process of preparing a gritand gel-free pigmented nitrocellulose coating composition by selective filtration which comprises uniformly suspending therein from 0.1 to 0.5 per cent'by departing from the spirit ofour invenweight of a diatomaceous filter aidehaving an in-* herent i permeability coefllcient of at least.

3.0x 10 and thereafter filtering the said pigmented nitrocellulose coating composition under pressure. I n

, 2. .The processor preparing a gritand gel-free pigmented nitrocellulose coating composition by selective filtration .wliich comprises uniformly suspending therein from 0.1 to 0.5 percent-by weight of a diatomaceous filter aid having an ln-- herent permeability coefiic'ient in the rangev of about 3.0 10- to 4.5 1n and thereafter filtering the said pigmented-nitrocellulose coating composition under pressure.

3. The process of preparing a gritand gel-free selective filtration'which comprises uniformly suspending-therein from 0.1 to 0.5 per cent by weight of a diatomaceous filter aid having an inthe filtering medium, this "material having an average particle size of 5 microns or less. In

addition to passing the useful pigment particles,

while retaining oversize particles, the use of the filter aid traps the gelatinous particles-so that the pores of the filtering medium are kept open for a much longerfiltering period, enabling increased average fiow rates and markedly increased v total throughputs of enamel. gHeretofore it has been practically impossible to use one of the most common types of filter presatheplate and frame I press (Shriver press) because of the extremely v rapid clogging of the filter cloth by the gelatinous material present in solutions of nitrocellulose. This situation existed even though it wa standpressure.

herent permeability coefficient in therange of about 30x10? to 4.0X105, and thereafter filtering the said pigmented nitrocellulose coating compositionu'nder' pressure. 1 e

4. The process of preparing a gritand gel-free pigmented nitrocellulose coating composition by selective filtration which comprises uniformly suspending therein from 0.1 to 0.5 per cent by weight of a diatomaceous filter aid having an inherent permeability 'coeflicient' 'of at least 3.4X10-, and thereafter filtering the said pigmented nitrocellulose coating composition under CARROL A. DoRAN.

" CLARENCE R. DE BOW, JR.

The filter cake pro'-'- 

